EP0881249B1 - Siloxane-polyether copolymers with unsaturated functionalities, and process for making them - Google Patents
Siloxane-polyether copolymers with unsaturated functionalities, and process for making them Download PDFInfo
- Publication number
- EP0881249B1 EP0881249B1 EP98109372A EP98109372A EP0881249B1 EP 0881249 B1 EP0881249 B1 EP 0881249B1 EP 98109372 A EP98109372 A EP 98109372A EP 98109372 A EP98109372 A EP 98109372A EP 0881249 B1 EP0881249 B1 EP 0881249B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polysiloxane
- polyether
- sir
- group
- siloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/10—Equilibration processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
Definitions
- the present invention relates to siloxane - polyether compositions with unsaturated functionalities, such as alkenyl and alkynyl groups, which are capable of being hydrosilylated. These compositions are useful as hydrophilic additives for addition -cure polysiloxane gels, elastomers and coatings.
- Siloxane - polyether copolymers may be linear, branched, hydrolyzable or nonhydrolyzable structures.
- U.S. Patent Nos. 4,657,959 and 4,752,633 disclose their use as semipermanent hydrophilic additives in dental impressions.
- EP-A-0 384 699 discloses fluoroorganopolysiloxanes that may be useful as a raw material for heat-vulcanization type fluorosilicone rubber.
- GB-A-2 154 596 discloses a process for the continuous polymerization of polydiorganosiloxanes.
- Polydiorganosiloxane having terminal or pendant unsaturated hydrocarbon groups are known. Typical examples are the linear polydimethylsiloxanes having a vinyl group attached to the silicon atom at each terminus of the chains, and the linear polydimethylsiloxanes with vinyl groups randomly distributed on silicon atoms in the chains. Polysiloxane - polyether copolymers bearing terminal methacrylate groups impart durable hydrophilicity to the contact lens compositions of U.S. Patent Nos. 4,259,467 and 4,260,725.
- U.S. Patent No. 5,580,921 discloses storage-stable polysiloxane compositions which impart permanent hydrophilicity to addition cure dental impression compounds.
- Permanent hydrophilicity is provided by polysiloxane - polyether copolymers which have 10 - 400 silicon atoms per molecule, which contain unsaturated functionalities and which are free of noble metal catalysts. The copolymers become bound to the polysiloxane matrix by Si-C bonds during the curing step. Synthesis of the copolymers comprises the preparation of a distillable silane - polyether compound followed by its hydrolysis, condensation and equilibration with alkenyl siloxanes.
- the copolymer chain lengths are greater than 10 and are miscible with the ⁇ , ⁇ -divinylpolysiloxanes used in addition cure formulations. This feature facilitates storage stability of the two part formulations and avoids the need to use the copolymer as a separate component. However, the copolymers of long siloxane chain length do not afford the most rapid spreading of water and wetting of the cured polysiloxane surface.
- the instant invention discloses noble metal-containing, unsaturated siloxane - polyether copolymer compositions synthesized by the base-catalyzed equilibration of unsaturated silanes and siloxanes with saturated siloxane - polyether copolymers or ring opening of cyclic siloxane polyether copolymers with unsaturated siloxanes.
- Base-catalyzed equilibration of an alkenyl silane or siloxane with siloxane - polyether copolymer products affords unsaturated siloxane - polyether copolymers which impart permanent hydrophilicity to addition cure polysiloxane compositions, as well as to polyethylene, polypropylene and polyester matrices.
- the equilibration reaction mixtures also contain polyethers and noble metal catalyst residues.
- Another object of the instant invention is the provision of unsaturated siloxane - polyether copolymers useful as hydrophilic modifiers in polysiloxane, polyethylene, polypropylene, polyester and other thermoplastic substrates.
- a still further object is control of the content of unsaturated groups in the hydrophilic modifier so that both desirable hydrophilicity and optimum catalysis (cure time and working time) are realized in addition cure polysiloxane compositions.
- Another aspect of the invention is products of the reactions set forth below, particularly those products in which there are up to five silicon atoms present.
- the polyether and siloxane segments are linked by Si-C bonds, which are resistant to cleavage under aqueous acidic and alkaline conditions.
- a method for the synthesis of the said unsaturated polysiloxane - polyether copolymers of controlled unsaturation content includes the following steps:
- the polysiloxane - polyether copolymer may be obtained, for example by hydrosilylation as described in U.S. Patent Nos. 3,299,112, 4,847,398, 4,857,583, 5,191,103 or 5,159,096, all of which are incorporated herein by reference, or from commercial sources.
- the copolymer can contain bound and free platinum, unreacted polyether and reaction byproducts such as acetals and propanal.
- the copolymer may be cyclic, linear, or branched (in either T or Q configuration). The exact structure of the copolymers for use herein will depend on the desired end structures, examples of which are set forth below.
- the copolymer may be represented by the formula [R 3 SiO 1 ⁇ 2 ] m [ZR 2 SiO 1 ⁇ 2 ] n [O 1 ⁇ 2 Si(R 2 )O 1 ⁇ 2 ] o [O 1 ⁇ 2 SiRZO 1 ⁇ 2 ] p [SiO 3/2 R] q [SiO 4/2 ] r wherein
- the copolymer is reacted with the saturated polyether-siloxane copolymer and silanes bearing non-aromatic unsaturated groups bonded to silicon through an Si-C bond so that either a redistribution of saturated and unsaturated groups occurs, or siloxane segments bearing unsaturated groups become incorporated into the polysiloxane blocks of the polysiloxane - polyether copolymers. If ethylenic, the unsaturation is ⁇ , ⁇ , while if the unsaturation is acetylenic, it may be internal to the unsaturated substituent.
- the siloxanes may be of the structure of the siloxane above, excpet that Z is replaced with R 1 .
- R 1 is a C 1 - C 20 , preferably C 1 - C 12 , unsaturated monovalent organic group that can be hydrosilylated to yield silicon - carbon bonds.
- Illustrative of the unsaturated groups represented by R 1 are the alkenyl groups (for example, vinyl, allyl, methallyl, vinylcyclohexanyl), and, the alkynyl groups (for example, acetylenic and propargyl).
- Equations (1 - 3) exemplify the chemical transformations expected.
- Catalysts containing the tetramethyl ammonium cation, or another tetra alkyl ammonium cation, are preferred because they are readily destroyed by heat at the end of the reaction.
- Neutralization with (CH 3 ) 3 SiCl or with strong acid (for example, HCl) is preferred when catalysts containing the alkali or alkaline earth metals are used.
- the base should be present at a catalytically effective amount, which generally is 0.05 wt % to 5 wt %, preferably 0.1 wt % to 1 wt %.
- the stoichiometric ratio of unsaturated siloxane to polysiloxane - polyether copolymer during the equilibration or ring opening covers the broad range, 0.05 - 20, but is preferably 0.5 - 4 and most preferably 0.75 - 3.
- the stoichiometric ratio is desirably 1 - 2. It is not necessary that every molecule of unsaturated siloxane - polyether copolymer be at least doubly substituted with hydrosilylatable alkenyl or alkynyl groups.
- a high content of unsaturation can lead to inhibition of cure when the unsaturated polysiloxane - polyether copolymer is used in addition cure polysiloxane formulations.
- That the reaction product contains hydrosilylatable unsaturated groups bound to silicon can be established and quantified by spectroscopic measurements, particularly 13 C and 29 Si nuclear magnetic resonance. These unsaturated groups are distinguishable from others such as allyl and propenyl, which are associated with unreacted polyether.
- a preferred process is one wherein the starting siloxane-polyether copolymer is cyclic (m, n, q, and r are all 0] which is ring opened with a disiloxane of the structure R 1 R 2 SiOSiR 2 R 1 or R 3 SiOSiR 2 R 1 (preferably, the former) with R and R 1 as above.
- Unsaturated siloxane - polyether copolymers are the principal products of the two step synthesis.
- the remainder of the reaction mixture comprises saturated siloxane - polyether copolymers, unreacted polyethers such as allyl, propenyl, methallyl, vinyl and propargyl polyethers, and free and/or chemically bound platinum.
- unreacted polyethers such as allyl, propenyl, methallyl, vinyl and propargyl polyethers
- platinum content of the unsaturated polysiloxane - polyether product can be in the range 0.5 - 100 ppm, but is typically 5 - 50 ppm.
- compositions comprise unsaturated polysiloxane - polyether copolymers having general formulae and polymer architectures set forth hereinbelow.
- R, R 1 and Z are as above.
- the groups R 2 may be the same as R or as R 1 . Thus, for example, they provide for the presence of methyl and vinyl groups on the same silicon atom, or for the existence of geminal divinyl substitution.
- the subscript, n has a value of 0 to 100, and preferably 0 to 50 inclusive.
- the subscript, m is greater than zero, but less than 50 and is preferably 1 to 12 in value.
- the subscript, p has a value of 0 to 25 and is preferably 1 to 6.
- the subscript, q is 1 up to about 100 and is preferably 10 to 50.
- the subscript, v has values of 0 to 3.
- Hydrophilicity may be determined by measuring the contact angle of a water drop on the surface of interest (see W. Noll, Chemistry and Technology of Silicones, Academic Press, NY, 1968, pp 447-452). A value less than about 60° after 2 - 3 minutes wetting time denotes a hydrophilic surface. It is known in the art that unmodified polysiloxane surfaces are very hydrophobic and yield water contact angles greater than about 80°. Commercially available hydrophilic dental impression materials yield values in the range, 40 - 60°. However, these hydrophilic values increase to the hydrophobic range following washing and/or disinfection of the dental impression.
- the unsaturated polysiloxane - polyether copolymers of the instant invention confer permanent hydrophilicity characterized by water contact angles that are less than about 50° before and after washing and/or disinfection.
- the contact angle is a thermodynamic quantity and should have a unique value for a particular system under special conditions. However, hysteresis is often found in contact angle measurements depending on the direction of movement of the interface relative to its interacting surface.
- the advancing contact angle typically designated ⁇ A
- the receding contact angle typically designated ⁇ R .
- ⁇ A ⁇ ⁇ ⁇ ⁇ R .
- Advancing and receding angles may differ by as much as 60°.
- ⁇ A for water in contact with silicones is greater than 120°.
- hydrophilicity is indicated by ⁇ A less than about 100°.
- Trimethylsiloxy terminated polysiloxane - polyether copolymers shown in Table 1 were prepared by hydrosilylation using the procedures of the patents cited in the table.
- TABLE 1 POLYSILOXANE - POLYETHER COPOLYMERS USED AS STARTING MATERIALS PRODUCT SILOXANE BACKBONE POLYETHER SYNTHESIS METHOD
- a MD'M H 2 C CHCH 2 (EO) 7.5 OCH 3 U.S. 3,299,112
- MD'M H 2 C CHCH 2 (EO) 5.5 (PO) 2.8 OH U.S. 5,191,103
- MD 4 D'M H 2 C CHCH 2 (EO) 3.23 OCH 3 U.S.
- Hydrophilicity was evaluated by measuring the water contact angle, as a function of time, on the surfaces of cured polysiloxane discs containing the unsaturated polysiloxane - polyether copolymers of this invention. Contact angles were also measured on control discs made without the inventive hydrophilic additives and on samples made from commercial compositions advertized as being hydrophilic. All measurements were made with a Ramé-Hart goniometer (Model 100 00 115). Standard deviations of the measured angles were ⁇ 5°.
- Dynamic contact angle measurements were made with a Cahn DCA-315 dynamic contact angle analyzer. The two part formulation was mixed and applied to the glass plate of the analyzer. Measurements were taken while the formulation was curing. Calculation of the advancing and receding contact angles were made automatically by the analyzer software.
- Examples 1 - 14 illustrate the synthesis of vinyl-containing polysiloxane - polyether copolymers by the general procedure described above. Reaction stoichiometry was varied as shown in Table 2 using the quantities of saturated polysiloxane - polyether copolymers of Table 1 and 1,3-divinyltetramethyldisiloxane (M*M*). All reactions were run at 85 - 90°C/4hr prior to catalyst decomposition and separation of volatiles.
- the reaction products varied in color from colorless to yellow to dark brown.
- This example illustrates the permanent hydrophilicity of selected unsaturated polysiloxane - polyether copolymers when they were incorporated into addition cure polysiloxane compositions.
- the unsaturated polysiloxane - polyether copolymers were tested in commercial two part dental formulations and in an unfilled formulation suitable for encapsulating electronic components or coating textiles and medical devices. Descriptions of the formulations and the quantities of hydrophilic additives used are given in Tables 4 - 6. TABLE 4 LIST OF COMMERCIAL DENTAL IMPRESSION MATERIALS TESTED DENTAL FORMULATION MANUFACTURER DESCRIPTION 3M EXPRESSTM 3M Dental Products Type I impression putty material.
- the unfilled formulation of Table 5 was cured by mixing either equal weights of the two parts, or by mixing in the weight ratio 1.5 PART A to 1.0 PART B , pouring the mixture in a cylindrical mold and heating in an oven at 120°C for 15 - 30 min. Water contact angles of the cured formulations with and without the hydrophilic, unsaturated polysiloxane - polyether copolymers were measured before and after disinfection of the cured discs. Comparisons were made with commercial hydrophilic dental formulations (Bisico S4i hydrophil and IMPREGUM® F).
- Table 6 shows that IMPREGUM® F is permanently hydrophilic in that its 3 minute water contact angles are 48 - 52° before and after disinfection.
- the Bisico S4i hydrophilic wash and J/P CORRECTTM Type III Light Extra samples all showed at least 10° post-infection increases in contact angles indicating loss of hydrophilicity. Contact angles increased to > 60°. All of the control polysiloxane compositions were hydrophobic; they yielded 3 or 10 minute water contact angles that were greater than 75°. There was little change in the values following disinfection.
- This example illustrates the durable hydrophilicity imparted to cured polysiloxane compositions by the unsaturated copolymers prepared in Examples 13 and 14.
- Table 7 shows the 3 minute water contact angles on the cured elastomer before and after disinfection. Above 1.5 wt% use level of the hydrophilic additive of Example 13, there was no change in the contact angles after disinfection. For 0.6 wt% use level, the cured polysiloxane was still hydrophilic after disinfection, but the contact angle had increased from 13° to 49°. The hydrophilic additive of Example 14 gave similar results, except that no changes in contact angle were now observed above ⁇ 2 wt% use level. TABLE 7 PERMANENT HYDROPHILICITY OF CURED POLYSILOXANES CONTAINING HYDROPHILIC ADDITIVES OF EXAMPLES 13 AND 14 .
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Dental Preparations (AREA)
Description
- The present invention relates to siloxane - polyether compositions with unsaturated functionalities, such as alkenyl and alkynyl groups, which are capable of being hydrosilylated. These compositions are useful as hydrophilic additives for addition -cure polysiloxane gels, elastomers and coatings.
- Siloxane - polyether copolymers may be linear, branched, hydrolyzable or nonhydrolyzable structures. U.S. Patent Nos. 4,657,959 and 4,752,633 disclose their use as semipermanent hydrophilic additives in dental impressions. EP-A-0 384 699 discloses fluoroorganopolysiloxanes that may be useful as a raw material for heat-vulcanization type fluorosilicone rubber. GB-A-2 154 596 discloses a process for the continuous polymerization of polydiorganosiloxanes.
- Polydiorganosiloxane having terminal or pendant unsaturated hydrocarbon groups are known. Typical examples are the linear polydimethylsiloxanes having a vinyl group attached to the silicon atom at each terminus of the chains, and the linear polydimethylsiloxanes with vinyl groups randomly distributed on silicon atoms in the chains. Polysiloxane - polyether copolymers bearing terminal methacrylate groups impart durable hydrophilicity to the contact lens compositions of U.S. Patent Nos. 4,259,467 and 4,260,725. Aoki, et al., Macromolecules, Rapid Communications, 18 (1997) 31 - 36 , synthesized hydrolyzable siloxane - polyether copolymers of general formula, [(R'2SiO)-(C2H4O)7]20-35, wherein R' = vinyl. While all of these functionalized polysiloxane - polyether copolymers can be reacted into polymer matrices or onto surfaces to improve hydrophilicity, water absorption, lubricity and/or adhesion, the reactions do not result in the formation of Si-C bonds between the matrix or substrate and the functionalized polysiloxane - polyether. Si-C bonds are desirable because they are strong and nonhydrolyzable.
- U.S. Patent No. 5,580,921 discloses storage-stable polysiloxane compositions which impart permanent hydrophilicity to addition cure dental impression compounds. Permanent hydrophilicity is provided by polysiloxane - polyether copolymers which have 10 - 400 silicon atoms per molecule, which contain unsaturated functionalities and which are free of noble metal catalysts. The copolymers become bound to the polysiloxane matrix by Si-C bonds during the curing step. Synthesis of the copolymers comprises the preparation of a distillable silane - polyether compound followed by its hydrolysis, condensation and equilibration with alkenyl siloxanes. The copolymer chain lengths are greater than 10 and are miscible with the α, ω-divinylpolysiloxanes used in addition cure formulations. This feature facilitates storage stability of the two part formulations and avoids the need to use the copolymer as a separate component. However, the copolymers of long siloxane chain length do not afford the most rapid spreading of water and wetting of the cured polysiloxane surface.
- Accordingly, the instant invention discloses noble metal-containing, unsaturated siloxane - polyether copolymer compositions synthesized by the base-catalyzed equilibration of unsaturated silanes and siloxanes with saturated siloxane - polyether copolymers or ring opening of cyclic siloxane polyether copolymers with unsaturated siloxanes. Base-catalyzed equilibration of an alkenyl silane or siloxane with siloxane - polyether copolymer products affords unsaturated siloxane - polyether copolymers which impart permanent hydrophilicity to addition cure polysiloxane compositions, as well as to polyethylene, polypropylene and polyester matrices. Besides the hydrophilic modifiers, the equilibration reaction mixtures also contain polyethers and noble metal catalyst residues.
- It is an object of the instant invention to provide unsaturated, nonhydrolyzable siloxane - polyether copolymers that are capable of forming further Si-C bonds via hydrosilylation. Another object of the instant invention is the provision of unsaturated siloxane - polyether copolymers useful as hydrophilic modifiers in polysiloxane, polyethylene, polypropylene, polyester and other thermoplastic substrates. A still further object is control of the content of unsaturated groups in the hydrophilic modifier so that both desirable hydrophilicity and optimum catalysis (cure time and working time) are realized in addition cure polysiloxane compositions. Another aspect of the invention is products of the reactions set forth below, particularly those products in which there are up to five silicon atoms present. In nonhydrolyzable siloxane - polyether copolymers, the polyether and siloxane segments are linked by Si-C bonds, which are resistant to cleavage under aqueous acidic and alkaline conditions.
- A method for the synthesis of the said unsaturated polysiloxane - polyether copolymers of controlled unsaturation content includes the following steps:
- (a) combining polysiloxane - polyether copolymers having the formula as set forth below and an alkenyl or alkynyl silane or siloxane, capable of undergoing addition or redistribution reactions with the copolymers in an amount sufficient to achieve the desirable degree of alkenyl or alkynyl substitution to form a first mixture,
- (b) adding to the first mixture of reagents a catalytically effective amount of a basic catalyst to form a reaction mixture; and
- (c) heating the reaction mixture.
- The polysiloxane - polyether copolymer may be obtained, for example by hydrosilylation as described in U.S. Patent Nos. 3,299,112, 4,847,398, 4,857,583, 5,191,103 or 5,159,096, all of which are incorporated herein by reference, or from commercial sources. The copolymer can contain bound and free platinum, unreacted polyether and reaction byproducts such as acetals and propanal. The copolymer may be cyclic, linear, or branched (in either T or Q configuration). The exact structure of the copolymers for use herein will depend on the desired end structures, examples of which are set forth below.
-
- R is a C1 - C20, preferably C1 - C12, saturated, monovalent organic group. Illustrative of the saturated monovalent groups represented by R are the alkyl groups (for example, methyl, ethyl, isopropyl, octyl and dodecyl groups), the aryl groups (for example, the phenyl and naphthyl groups), the alkaryl groups (for example, tolyl and nonylphenyl groups), the aralkyl groups (for example, benzyl and phenethyl groups) and the cycloalkyl groups (for example, cyclopentyl and cyclohexyl groups). R may also be a functionalized organic group such as the chloropropyl, heptafluoroisopropyl, and cyanoethyl groups. Most preferably R is methyl.
- Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond. Z has general formulae of the type, -CxH2xO(CaH2aO)bR" and -CxH2xOG[(CaH2aO)bR"]r wherein x is an integer in the range 1 - 2b, and is preferably 2 - 8. The subscript, a, is an integer having a value greater than or equal to 2. Preferred values of a are 2, 3, and 4. Illustrative of the oxyalkylene groups in the polyether portion of the copolymer are the oxyethylene, the oxy-1,2-propylene, oxy-1,2-butylene, oxy-2,2-dimethyl-1,3-propylene groups and the like. The polyether portion of the copolymer may contain oxyalkylene units of more than one type. For optimum hydrophilicity, it is desirable that at least 40 weight percent, and preferably at least 70 weight percent, of the oxyalkylene groups be oxyethylene groups. The subscript, b, is a positive number that is preferably greater than 3 up to 12.
- G is a polyhydroxy group capable of being alkoxylated. The subscript, r, represents the number of alkoxylated hydroxyl groups. Examples of G are alkylene glycols, alkyne glycols, glycerol, pentaerythritol, hydroquinone, trimethylolpropane, sorbitol, glucose and sucrose.
- R" is hydrogen or a polyether capping group such as an alkyl group of 1 - 8 carbon atoms, or an acyl group of 1 - 8 carbon atoms, or a vinyl ether or an organosilyl group. Alkyl groups exemplifying R" are methyl, tertiary butyl and 2-ethylhexyl. Examples of acyl capping groups are acetoxy, acetoacetoxy, acryloxy, methacryloxy and benzoyl. Organosilyl capping groups comprise the saturated trialkylsilyl groups such as trimethylsilyl, triethyl, ethylisopropyl, thexyldimethyl, t-butyldimethyl, t-butyldiphenyl, the unsaturated capping groups such as the vinyldimethyl, divinyloctyl, ethynyldimethyl and propynyldimethyl. Examples of vinyl ether end groups comprise dihydropyranyl and vinyloxyethoxy (H2C=CH-O-CH2CH2O-). Owing to the variable efficiency of polyether capping reactions, uncapped polyether molecules are likely to be present during the hydrosilylation synthesis of the polysiloxane - polyether copolymer starting material. Accordingly, nominally capped copolymer products may also contain uncapped polysiloxane - polyether copolymers.
- m = 0 to 5, preferably 0 to 2; n = 0 to 3; preferably 0; o = 0 to 100, preferably 0 to 50; p = 0 to 30; preferably 0 to 10; q = 0 to 4; r = 0 to 2. If p = 0, then n>0 and if n = 0, then p > 0. m + n + o + p + q + r = 3 to 100, preferably 3 to 50, most preferably 3 to 5.
- The copolymer is reacted with the saturated polyether-siloxane copolymer and silanes bearing non-aromatic unsaturated groups bonded to silicon through an Si-C bond so that either a redistribution of saturated and unsaturated groups occurs, or siloxane segments bearing unsaturated groups become incorporated into the polysiloxane blocks of the polysiloxane - polyether copolymers. If ethylenic, the unsaturation is α, β, while if the unsaturation is acetylenic, it may be internal to the unsaturated substituent. The silanes may be represented by the formula RaR1 bSi(OR)4-a-b with a=1 to 3, b=1 to 3 and a + b ≤ = 3. The siloxanes may be of the structure of the siloxane above, excpet that Z is replaced with R1. R1 is a C1 - C20, preferably C1 - C12, unsaturated monovalent organic group that can be hydrosilylated to yield silicon - carbon bonds. Illustrative of the unsaturated groups represented by R1 are the alkenyl groups (for example, vinyl, allyl, methallyl, vinylcyclohexanyl), and, the alkynyl groups (for example, acetylenic and propargyl). Specific examples of the siloxane/silane are [H2C=CHSi(CH3)2]2O or [H2C=CHSi(CH3)O]3-25 , or (H2C=CH) x Si[OSi(CH3)3]4-x , (H2C=CH) x Si(OC2H4OCH3)4-x , x = 1, 2, or 3).
-
- Redistribution is accomplished in the presence of basic catalysts such as KOH, CsOH, Ca(OH)2, (CH3)4N+ -OSi(CH3)3 , (CH3)4N+ -[OSi(CH3)2]sO- +N(CH3)4 (s = 4 - 100) and K+ -OSi(CH3)3 at temperatures up to about 200°C, preferably up to about 150°C. Catalysts containing the tetramethyl ammonium cation, or another tetra alkyl ammonium cation, are preferred because they are readily destroyed by heat at the end of the reaction. The reaction mixture may be stripped in vacuo to remove unreacted alkenyl siloxane and volatile by-products of the thermal decomposition such as trimethylamine and redistribution by-products such as (CH3)3SiOH, (CH3)3SiOSi(CH3)3 and H2C=CHSi(CH3)2OSi(CH3)3. Neutralization with (CH3)3SiCl or with strong acid (for example, HCl) is preferred when catalysts containing the alkali or alkaline earth metals are used. Thereafter, the reaction mixture is subjected to filtration and in vacuo stripping of volatiles. The base should be present at a catalytically effective amount, which generally is 0.05 wt % to 5 wt %, preferably 0.1 wt % to 1 wt %.
- The stoichiometric ratio of unsaturated siloxane to polysiloxane - polyether copolymer during the equilibration or ring opening covers the broad range, 0.05 - 20, but is preferably 0.5 - 4 and most preferably 0.75 - 3. When a cyclic polysiloxane - polyether copolymer is used (as shown in Equation 3 above), the stoichiometric ratio is desirably 1 - 2. It is not necessary that every molecule of unsaturated siloxane - polyether copolymer be at least doubly substituted with hydrosilylatable alkenyl or alkynyl groups. It is only necessary that sufficient molecules be at least singly substituted so that they become bound to the matrix or substrate requiring permanent hydrophilicity. Thus, the addition reaction depicted in equation (3) can be done with mixtures of [(CH3)3Si]2O and [H2C=CHSi(CH3)2]2O to control the vinyl content of the product. In some instances, a high content of unsaturation can lead to inhibition of cure when the unsaturated polysiloxane - polyether copolymer is used in addition cure polysiloxane formulations. That the reaction product contains hydrosilylatable unsaturated groups bound to silicon can be established and quantified by spectroscopic measurements, particularly 13C and 29Si nuclear magnetic resonance. These unsaturated groups are distinguishable from others such as allyl and propenyl, which are associated with unreacted polyether.
- A preferred process is one wherein the starting siloxane-polyether copolymer is cyclic (m, n, q, and r are all 0] which is ring opened with a disiloxane of the structure R1R2SiOSiR2R1 or R3SiOSiR2R1 (preferably, the former) with R and R1 as above.
- Unsaturated siloxane - polyether copolymers are the principal products of the two step synthesis. The remainder of the reaction mixture comprises saturated siloxane - polyether copolymers, unreacted polyethers such as allyl, propenyl, methallyl, vinyl and propargyl polyethers, and free and/or chemically bound platinum. If the composition is prepared with uncapped polyethers, some of the copolymers and polyethers might be linked by acetal groups. The presence of acetals is not detrimental to the performance of the reaction product as a hydrophilic additive, but it is preferable to remove same. The platinum content of the unsaturated polysiloxane - polyether product can be in the range 0.5 - 100 ppm, but is typically 5 - 50 ppm.
- The compositions comprise unsaturated polysiloxane - polyether copolymers having general formulae and polymer architectures set forth hereinbelow.
-
- (A) R1-SiR2O(SiR2-O)n-(SiR2Z-O)m-SiR2R1
- (B) R1-SiR2O(SiR2-O)n-(SiR2Z-O)m-SiR3
- (C) R3SiO(SiR2-O)n-(SiR2Z-O)m-(SiR2R1-O)p-SiR3
- (D) R1-R2SiO(SiR2-O)n-(SiR2Z-O)m-(SiR2R1-O)p-SiR3
- (E) R1-R2SiO(SiR2-O)n-(SiR2Z-O)m-(SiR2R1-O)p-SiR2R1
- (F) Z-SiR2O(SiR2-O)n-(SiR2R1-O)p-SiR2R1
- (G) [Z-SiR2O(SiR2-O)n]q-(SiR2-O)-(SiR2R1-O)p-SiR2R1
-
- (H) (R2Si-O)n-(SiR2Z-O)m-(SiR2R1-O)p
-
- (I) R1Si[(O-SiR2)n- Z]3
- (J) RSi[(O-SiR2R1)p-(O-SiR2)n-Z]3
- (K) [R1SiR2O(SiR2-O)n]v-(SiO2)[(O-SiR2R1)p(O-SiR2Z)m]4-v
- R, R1 and Z are as above. The groups R2 may be the same as R or as R1. Thus, for example, they provide for the presence of methyl and vinyl groups on the same silicon atom, or for the existence of geminal divinyl substitution.
- The subscript, n, has a value of 0 to 100, and preferably 0 to 50 inclusive. The subscript, m, is greater than zero, but less than 50 and is preferably 1 to 12 in value. The subscript, p, has a value of 0 to 25 and is preferably 1 to 6. The subscript, q, is 1 up to about 100 and is preferably 10 to 50. The subscript, v, has values of 0 to 3.
- One preferred embodiment of the invention is compounds of any of the foregoing formulas (A) through (K), and particularly (A) through (G), wherein the total number of silicon atoms in the molecule is 3 to 5, i.e., R2R2SiO(SiR2O)n(SiR2ZO)m(SiR2R1O)pSiR2R2 wherein +m+p = 0 to 3, each n. m, and p are 0 to 3, with the proviso that there is at least one Z and at least one R2 per molecule and R2 is R, R1 or Z. Even more preferably, this a vinyl endblocked siloxane, with p=0 and R is methyl.
-
- Hydrophilicity may be determined by measuring the contact angle of a water drop on the surface of interest (see W. Noll, Chemistry and Technology of Silicones, Academic Press, NY, 1968, pp 447-452). A value less than about 60° after 2 - 3 minutes wetting time denotes a hydrophilic surface. It is known in the art that unmodified polysiloxane surfaces are very hydrophobic and yield water contact angles greater than about 80°. Commercially available hydrophilic dental impression materials yield values in the range, 40 - 60°. However, these hydrophilic values increase to the hydrophobic range following washing and/or disinfection of the dental impression. The unsaturated polysiloxane - polyether copolymers of the instant invention confer permanent hydrophilicity characterized by water contact angles that are less than about 50° before and after washing and/or disinfection.
- The contact angle is a thermodynamic quantity and should have a unique value for a particular system under special conditions. However, hysteresis is often found in contact angle measurements depending on the direction of movement of the interface relative to its interacting surface. When an interface advances along a fresh surface, the advancing contact angle (typically designated θA) is larger than the receding contact angle (typically designated θR). In general θA≥ θ ≥ θR. Advancing and receding angles may differ by as much as 60°. θA for water in contact with silicones is greater than 120°. For measurements made on fresh surfaces under dynamic conditions, hydrophilicity is indicated by θA less than about 100°.
- The following illustrative examples describe the instant invention in more detail. They are not intended to limit the scope of the specification and the claims. Abbreviations used in the description of the illustrative examples are defined in the following table.
ABBREV. MEANING ABBREV. MEANING M (CH3)3SiO1/2 ICP inductively coupled plasma spectroscopy D (CH3)2SiO2/2 gpc gel permeation chromatography D' CH3SiHO2/2 θ water contact angle M' (CH3)2SiHO1/2 gc/ms gas chromatography /mass spectrometry M* H2C=CH(CH3)2SiO1/2 MVC mixture of cyclic methylvinyl-siloxanes EO ethylene oxide ICP inductively coupled plasma spectroscopy PO propylene oxide gc gas chromatography BO butylene oxide - Trimethylsiloxy terminated polysiloxane - polyether copolymers shown in Table 1 were prepared by hydrosilylation using the procedures of the patents cited in the table.
TABLE 1 POLYSILOXANE - POLYETHER COPOLYMERS USED AS STARTING MATERIALS PRODUCT SILOXANE BACKBONE POLYETHER SYNTHESIS METHOD A MD'M H2C=CHCH2(EO)7.5OCH3 U.S. 3,299,112 B MD'M H2C=CHCH2(EO)5.5(PO)2.8OH U.S. 5,191,103 C MD4D'M H2C=CHCH2(EO)3.23OCH3 U.S. 4,847,398 D MD8D'M H2C=CHCH2(EO)3.23OH U.S. 5,191,103 E MD8D'M H2C=CHCH2(EO)3OCH3 U.S. 3,507,815 F MD8D'M H2C=CHCH2(EO)12(PO)3OH U.S. 5,191,103 G MD12D'M H2C=CHCH2(EO)3.23OH U.S. 4,847,398 H MD12D'M H2C=CHCH2(EO)3OCH3 U.S. 3,507,815 I MD12D'M H2C=CHCH2(EO)12(PO)3OH U.S. 5,191,103 J MD16D'M H2C=CHCH2(EO)3.23OH U.S. 5,191,103 K MD16D'M H2C=CHCH2(EO)3OCH3 U.S. 3,507,815 L MD16D'M H2C=CHCH2(EO)12(PO)3OH U.S. 5,191,103 M D4D' H2C=CHCH2(EO)7.5OCH3 U.S. 3,507,815 N D4D' H2C=CHCH2(EO)5.5(PO)2.8OH U.S. 5,191,103 - 1,3-Divinyltetramethyldisiloxane (M*M*) was purchased from Gelest, Inc. A methylvinylcyclosiloxane mixture, [H2C=CH(CH3)SiO]p, p = 3 (4.3 wt%), p = 4 (76.54 wt%), p = 5 (17.68 wt%), p = 6 (1.4 wt%) was prepared by hydrolysis of H2C=CH(CH3)SiCl2. Cyclo(dimethylsiloxane-co-methylhydrogenosiloxanes) of the type D n D' m (n = 1 - 5, m= 1 - 4, n + m < 8) were prepared by the acid-catalyzed equilibration of polydimethylsiloxanes and polymethylhydrogensiloxanes as described by Chang and Buese in Polymer Preprints , 33 (1992) 160 - 161.
- SILWET® L-77 is a siloxane - polyether copolymer with terminal trimethylsiloxy groups.
- V-2K is an α, ω-divinylpolydimethylsiloxane having 0.22 wt% vinyl and a viscosity of 2000 cSt at 25°C.
- V-200 is a α, ω-divinylpolydimethylsiloxane with 0.7 wt% vinyl and a viscosity of 200 cSt at 25°C.
- V-XL is a crosslinker with SiH content 40 cc H2/g
- VCAT-RT is a platinum complex of 1,3-divinyltetramethyldisiloxane dissolved in 500 cSt silicone oil. Its Pt content is - 2 wt%.
- SILWET® L-77, V-2K, V-200, V-XL and VCAT-RT are products of Witco Corp.
- BANICIDE®, a glutaraldeyhde-based, sterilizing disinfectant manufactured by Pascal Co. Inc., was used as the disinfecting medium in accordance with the manufacturer's instructions.
- Disinfection time was overnight (- 16 hr) in most cases and in others as long as 64 hr.
- Commercial dental impression formulations were mixed and cured as directed in the manufacturer's product literature.
- (CH3)4N+ - OSi(CH3)2[OSi(CH3)2]58Si(CH3)2O- + N(CH3)4(N-CAT) was prepared by charging 216 g [(CH3)2SiO]4, 18.1 g (CH3)4NOH.5H2O and 250 g toluene to three-necked 1 L round bottom flask fitted with a temperature-controlled heating mantle, mechanical stirrer, Claisen connection, water cooled Friedrich condenser, thermometer, and vacuum take-off line. The mixture was heated to 65 - 70°C at 100 - 200 torr to remove the water - toluene azeotrope. When no additional azeotrope distilled over the water and toluene were separated and the weight of water (~ 8 g) recorded. The vacuum was released, the temperature was lowered and another 100 g toluene added to the flask. Final stripping of residual water (~ 1 g) and all of the toluene was accomplished by heating to 90°C at 50 torr. The product is a viscous, hygroscopic liquid.
- Equilibration and ring opening reactions were performed in a three-necked 500 mL round bottom flask fitted with a temperature-controlled heating mantle, mechanical stirrer, Claisen connection, water cooled Friedrich condenser, thermometer, and nitrogen sparge line. Weighed quantities of polysiloxane - polyether copolymer, vinylsiloxane and N-CAT were charged to the flask and the stirring contents heated to 90°C for 4 hours. The temperature was then increased to 140°C for 1 hour to decompose N-CAT and the reaction mixture was later stripped in vacuo at 100°C/4 torr for 4 hours. Condensate was collected, weighed and analyzed by gc and gc/ms. The stripped product was weighed and analyzed by 13C and 29Si nmr, gpc and ICP. It was used as a hydrophilic additive and as a silicone surfactant.
- Hydrophilicity was evaluated by measuring the water contact angle, as a function of time, on the surfaces of cured polysiloxane discs containing the unsaturated polysiloxane - polyether copolymers of this invention. Contact angles were also measured on control discs made without the inventive hydrophilic additives and on samples made from commercial compositions advertized as being hydrophilic. All measurements were made with a Ramé-Hart goniometer (Model 100 00 115). Standard deviations of the measured angles were ± 5°.
- Dynamic contact angle measurements were made with a Cahn DCA-315 dynamic contact angle analyzer. The two part formulation was mixed and applied to the glass plate of the analyzer. Measurements were taken while the formulation was curing. Calculation of the advancing and receding contact angles were made automatically by the analyzer software.
- Examples 1 - 14 illustrate the synthesis of vinyl-containing polysiloxane - polyether copolymers by the general procedure described above. Reaction stoichiometry was varied as shown in Table 2 using the quantities of saturated polysiloxane - polyether copolymers of Table 1 and 1,3-divinyltetramethyldisiloxane (M*M*). All reactions were run at 85 - 90°C/4hr prior to catalyst decomposition and separation of volatiles.
TABLE 2 SYNTHESIS OF VINYL-CONTAINING POLYSILOXANE - POLYETHER COPOLYMERS EXAMPLE Copolymer, g (see Table 1) M*M*, g N-CAT, g STRIPPED PRODUCT, g 1 A, 120.9 36 0.5 112 2 B, 132.6 36 0.5 124 3 C, 67.7 17.5 0.1 64.2 4 D, 82 15 0.1 83.5 5 E, 85 15 0.1 83.2 6 F, 53 10 0.1 55.1 7 G, 53 12 0.1 55.4 8 H, 55 12 0.1 57.2 9 I, 63 10 0.1 68.4 10 J, 86.5 10 0.1 92.1 11 K, 51.2 6 0.1 52.2 12 L, 50 4.3 0.1 52.5 13 M, 98.4 24 0.4 96.5 14 N, 98.6 21 0.4 100.2 - The reaction products varied in color from colorless to yellow to dark brown.
- This example illustrates the composition of the unsaturated polysiloxane - polyether copolymers of synthesized in Examples 1, 2, 13 and 14. The platinum content of the products was analyzed by ICP and found to be 10 - 40 ppm as shown below.
TABLE 3 EXAMPLE Pt, ppm 1 15 2 10 13 37 14 30 - 29Si and 13C nmr spectra of the reaction products of Examples 1 and 2 were recorded on a BRUKER ACP-300 spectrometer. The molar ratio of vinyldimethylsilyl endgroups (M*) to trimethylsilyl endgroups (M) in the product of Example 1 was 0.32 and in Example 2 was 0.24. It is clear from these analytical data that not all of the (CH3)3Si endgroups of the starting copolymer were converted to H2C=CHSi(CH3)2 endgroups. For example in Copolymer M, the ratio of silicon bound methyls to SiCH3 groups was 11.24, as compared to a theoretical value of 9.0. However, it will be illustrated below that the level of conversion realized was sufficient to impart permanent hydrophilicity to addition cure polysiloxane compositions.
- This example illustrates the permanent hydrophilicity of selected unsaturated polysiloxane - polyether copolymers when they were incorporated into addition cure polysiloxane compositions. The unsaturated polysiloxane - polyether copolymers were tested in commercial two part dental formulations and in an unfilled formulation suitable for encapsulating electronic components or coating textiles and medical devices. Descriptions of the formulations and the quantities of hydrophilic additives used are given in Tables 4 - 6.
TABLE 4 LIST OF COMMERCIAL DENTAL IMPRESSION MATERIALS TESTED DENTAL FORMULATION MANUFACTURER DESCRIPTION 3M EXPRESS™ 3M Dental Products Type I impression putty material. Very high viscosity Bisico S1a/S1b Bisico 72 Shore A impression putty material Blu-Mousse Parkell Biomaterials Thixotropic impression material J/P Q3 ™ Universal Jeneric®/Pentron®, Inc Type I high viscosity impression material J/P CORRECT™ VPS Jeneric®/Pentron®, Inc. Type III Light Extra, Light Viscosity COMPARATIVE Bisico S4i hydrophil Bisico Type I low viscosity, light body IMPREGUM® F Espe Type I polyether impression material TABLE 5 COMPOSITION OF UNFILLED FORMULATION INGREDIENT PART A, wt% PART B, wt% V-2K 86.8 91.53 V-200 - 8.18 V-XL 13.2 VCAT-RT - 0.12 MVC - 0.17 - The unfilled formulation of Table 5 was cured by mixing either equal weights of the two parts, or by mixing in the weight ratio 1.5 PART A to 1.0 PART B, pouring the mixture in a cylindrical mold and heating in an oven at 120°C for 15 - 30 min. Water contact angles of the cured formulations with and without the hydrophilic, unsaturated polysiloxane - polyether copolymers were measured before and after disinfection of the cured discs. Comparisons were made with commercial hydrophilic dental formulations (Bisico S4i hydrophil and IMPREGUM® F).
- Table 6 shows that IMPREGUM® F is permanently hydrophilic in that its 3 minute water contact angles are 48 - 52° before and after disinfection. However, the Bisico S4i hydrophilic wash and J/P CORRECT™ Type III Light Extra samples all showed at least 10° post-infection increases in contact angles indicating loss of hydrophilicity. Contact angles increased to > 60°. All of the control polysiloxane compositions were hydrophobic; they yielded 3 or 10 minute water contact angles that were greater than 75°. There was little change in the values following disinfection.
- Addition of 1.2 wt% of the unsaturated copolymer of Example 2 to the 3M dental putty in Example 16 effected a lowering of contact angles to < 20° before disinfection and to ≤ 25° afterwards. This dramatic and durable contact angle lowering compared to the control (~ 80°) was effected by unsaturated copolymer product containing 10 ppm Pt and the functional groups idenified by nmr spectroscopy in Table 3. The data confirm that the unsaturated polysiloxane - polyether copolymers in the product of Example 2 were permanently bonded to the cured matrix. Similar evidence for permanent hydrophilic modification with this product is seen in the data for J/P Q3 Universal (Ex. 18), for Bisico S1a/S1b (Ex. 20) and for the unfilled formulation (Ex. 21). The effective quantity of unsaturated polysiloxane - polyether copolymer employed in these Examples was 0.1 - 0.3 wt%.
- 0.5 - 2.0 wt% of the unsaturated polysiloxane - polyether copolymer product of Example 1 also imparted durable hydrophilicity to the commercial dental formulations in Examples 17, 19 and 24 and the unfilled formulation of Example 22. The effective quantity of unsaturated copolymer in these experiments was only 0.05 - 0.35 wt%. Thus, both the high efficacy and effectiveness of the inventive compositions in affording permanent hydrophilicity to polysiloxane compositions are established.
- This example illustrates the durable hydrophilicity imparted to cured polysiloxane compositions by the unsaturated copolymers prepared in Examples 13 and 14.
- The unfilled formulation of Table 5 was used in the weight ratio 1.5 PART A to 1.0 PART B. Use levels of the hydrophilic, unsaturated copolymers of Examples 13 and 14 were varied as shown in Table 7. Weight percent values shown are based on the total weight of PART A, PART B and hydrophilic additive in the experiment. Control samples without the hydrophilic additive were prepared and measured as a comparison.
- Table 7 shows the 3 minute water contact angles on the cured elastomer before and after disinfection. Above 1.5 wt% use level of the hydrophilic additive of Example 13, there was no change in the contact angles after disinfection. For 0.6 wt% use level, the cured polysiloxane was still hydrophilic after disinfection, but the contact angle had increased from 13° to 49°. The hydrophilic additive of Example 14 gave similar results, except that no changes in contact angle were now observed above ∼ 2 wt% use level.
TABLE 7 PERMANENT HYDROPHILICITY OF CURED POLYSILOXANES CONTAINING HYDROPHILIC ADDITIVES OF EXAMPLES 13 AND 14. EXAMPLE ADDITIVE USE LEVEL, wt% θ, BEFORE DISINFECTION θ, AFTER DISINFECTION 25 Example 13 0.6 13° 49° 26 1.5 12° 13° 27 2.0 12° 12° 28 3.0 11° 12° CONTROL NONE - 84° 85° 29 Example 14 0.5 32° 63° 30 1.1 15° 48° 31 2.2 14° 15° 32 2.8 12° 14° CONTROL NONE - 84° 85°
Claims (8)
- A process for making an unsaturated polysiloxane - polyether copolymer product comprising(a) adding to a polysiloxane -polyether copolymer having the formula [R3SiO½]m[ZR2SiO½]n [O½Si(R2)O½]o[O½SiRZO½]p[SiO3/2R]q[SiO4/2]r
wherein R is a C1 - C20, preferably C1 - C12, saturated, monovalent organic group, Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond, m = 0 to 5, n = 0 to 3; o = 0 to 100, p = 0 to 30; q = 0 to 4; r = 0 to 2 and if p = 0, then n>0 and if n = 0, then p > 0 and m + n + o + p + q + r = 3 to 100, an alkenyl or alkynyl silane or siloxane capable of undergoing an addition or redistribution reaction with the polysiloxane - polyether, in an amount sufficient to achieve the desired degree of alkenyl or alkynyl substitution on said polysiloxane - polyether copolymer;(b) adding to the mixture formed in step (a) a catalytically effective amount of a basic catalyst; and(c) heating the mixture formed in step (b) to a temperature up to 200°C, to effect reaction to form unsaturated polysiloxane - polyether copolymer product. - A process in accordance with claim 1 wherein said basic catalyst is selected from the group consisting of KOH, CsOH, Ca(OH)2, (CH3)4N+ -OSi(CH3)3, (CH3)4N+ -[OSi(CH3)2]sO-+N(CH3)4(wherein s = 4 - 100) and K+ -OSi(CH3)3.
- A process according to claim 1 wherein the copolymer is a cyclic structure which is ring opened with a disiloxane of the structure R1R2SiOSiR2R1 or R3SiOSiR2R1 with R1 is a C1 - C20, unsaturated monovalent organic group that can be hydrosilylated to yield silicon - carbon bonds R is a C1 - C20 saturated, monovalent organic group.
- A process according to claim 3 wherein R1 is a vinyl group.
- A siloxane of the structure: R2R2SiO(SiR2O)n(SiR1ZO)m(SiR1RO)pSiR2R2 wherein n +m+p = 0 to 3, each n, m, and p are 0 to 3, with the proviso that there is at least one Z and at least one R1 per molecule and wherein R1 is a C1 - C20, unsaturated monovalent organic group that can be hydrosilylated to yield silicon - carbon bonds, R is a C1 - C20 saturated, monovalent organic group; Z is a polyether-containing group that is linked to the polysiloxane block by a silicon-carbon bond and R2 is selected from the group consisting of R, R1 and Z.
- A siloxane according to claim 5 wherein Z is CxH2xO(CaH2aO)bR" or - CxH2xOG[(CaH2aO)bR'']r wherein x is an integer in the range 1 - 20, G is a polyhydroxy group capable of being alkoxylated, a is 2 to 4, b = 3 to 12, R" is hydrogen or a polyether capping group, and r, represents the number of alkoxylated hydroxyl groups on the G group.
- A siloxane according to claim 6 wherein R2 is vinyl and p=0.
- A siloxane according to claim 7 wherein each R is methyl.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4771997P | 1997-05-27 | 1997-05-27 | |
US47719P | 1997-05-27 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0881249A2 EP0881249A2 (en) | 1998-12-02 |
EP0881249A3 EP0881249A3 (en) | 1999-01-27 |
EP0881249B1 true EP0881249B1 (en) | 2005-09-21 |
Family
ID=21950543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98109372A Expired - Lifetime EP0881249B1 (en) | 1997-05-27 | 1998-05-22 | Siloxane-polyether copolymers with unsaturated functionalities, and process for making them |
Country Status (8)
Country | Link |
---|---|
US (1) | US6103847A (en) |
EP (1) | EP0881249B1 (en) |
JP (1) | JP4201385B2 (en) |
KR (1) | KR100501141B1 (en) |
BR (1) | BR9801709A (en) |
CA (1) | CA2238556C (en) |
DE (1) | DE69831627T2 (en) |
SG (1) | SG66469A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014200106A1 (en) | 2013-02-13 | 2014-08-14 | Evonik Industries Ag | Producing functional group-containing polysiloxane useful e.g. as component of dental impression compounds, comprises reacting terminal hydroxy functional, polysiloxane, alkoxysilanes, and water in the presence of Bronsted-acidic compound |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0924239B1 (en) * | 1997-12-22 | 2004-11-24 | General Electric Company | Durable hydrophilic coating for textiles |
US7241009B2 (en) * | 2001-11-21 | 2007-07-10 | Calhoun Vision, Inc. | Crosslinking of silicones presence of functionalized silicones |
US20050027032A1 (en) * | 2003-07-18 | 2005-02-03 | Hare Robert V. | Polyorganosiloxane dental impression materials |
CA2632004A1 (en) * | 2005-12-07 | 2007-06-14 | Momentive Performance Materials Inc. | Composition for separating mixtures |
US20070125716A1 (en) * | 2005-12-07 | 2007-06-07 | Ian Procter | Process for separating mixtures |
DE102006001126A1 (en) * | 2006-01-09 | 2007-07-12 | Kettenbach Gmbh & Co. Kg | Dental impression compounds, hardened products prepared therefrom and use of surfactants for the production of dental impression compounds |
US20070249502A1 (en) * | 2006-04-24 | 2007-10-25 | Ian Procter | Composition for separating mixtures |
DE102010028182A1 (en) | 2010-04-26 | 2011-10-27 | Momentive Performance Materials Gmbh | Hydrophilic polyorganosiloxanes |
JP5960955B2 (en) | 2010-12-03 | 2016-08-02 | 現代自動車株式会社Hyundai Motor Company | Vehicle capacitors |
US9657143B2 (en) * | 2012-12-26 | 2017-05-23 | Cheil Industries, Inc. | Curable polysiloxane composition for optical device and encapsulant and optical device |
CN112280046B (en) * | 2020-11-13 | 2022-10-21 | 杭州崇耀科技发展有限公司 | Preparation method of alkyne bond-containing polyether modified organic silicon |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL133334C (en) * | 1964-06-19 | 1900-01-01 | ||
IT987394B (en) * | 1972-05-24 | 1975-02-20 | Gen Electric | SILICONE FLUIDS CONTAINING HYDROCARBUS GROUPS USEFUL AS HYDRAULIC FLUIDS |
US4260725A (en) * | 1979-12-10 | 1981-04-07 | Bausch & Lomb Incorporated | Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains |
US4259467A (en) * | 1979-12-10 | 1981-03-31 | Bausch & Lomb Incorporated | Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains |
US4551515A (en) * | 1984-02-27 | 1985-11-05 | General Electric Company | Process for the continuous manufacture of silicone gums |
US4657959A (en) * | 1985-11-15 | 1987-04-14 | Minnesota Mining And Manufacturing Company | Hydrophilic silicones |
US4752633A (en) * | 1985-11-15 | 1988-06-21 | Minnesota Mining And Manufacturing Co. | Ethoxylated siloxane surfactants and hydrophilic silicones prepared therewith |
US4857583A (en) * | 1987-07-02 | 1989-08-15 | Union Carbide Corporation | Process for the preparation of organopolysiloxane surfactants |
US4988504A (en) * | 1987-08-19 | 1991-01-29 | General Electric Company | Silicone surfactants |
US4847398A (en) * | 1987-09-09 | 1989-07-11 | Union Carbide Corporation | Process for the preparation of siloxane-oxyalkylene copolymers |
JPH0618880B2 (en) * | 1989-02-21 | 1994-03-16 | 信越化学工業株式会社 | Fluoroorganopolysiloxane and method for producing the same |
DE4129613A1 (en) * | 1991-09-06 | 1993-03-11 | Wacker Chemie Gmbh | STORAGE-RESISTANT, PERMANENTLY WET-WETTABLE VULCANISATE-RESULTING POLYSILOXANE |
US5159096A (en) * | 1991-09-30 | 1992-10-27 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the preparation of siloxane-oxyalkylene copolymers |
US5191103A (en) * | 1991-12-30 | 1993-03-02 | Union Carbide Chemicals & Plastics Technology Corporation | Process and composition for promoting hydrosilylation reactions using sterically hindered nitrogen-containing and phosphorus-containing compounds |
GB2278846B (en) * | 1993-06-10 | 1997-04-16 | Gen Electric | Fluorosilicone terpolymeric fluid |
US5565194A (en) * | 1994-03-04 | 1996-10-15 | Th. Goldschmidt Ag. | Polysiloxane-polyoxyalkylene block copolymers and their use as additives for hair cosmetics |
-
1998
- 1998-05-21 US US09/082,563 patent/US6103847A/en not_active Expired - Lifetime
- 1998-05-22 SG SG1998001126A patent/SG66469A1/en unknown
- 1998-05-22 DE DE69831627T patent/DE69831627T2/en not_active Expired - Lifetime
- 1998-05-22 EP EP98109372A patent/EP0881249B1/en not_active Expired - Lifetime
- 1998-05-25 CA CA002238556A patent/CA2238556C/en not_active Expired - Fee Related
- 1998-05-26 KR KR10-1998-0018986A patent/KR100501141B1/en not_active IP Right Cessation
- 1998-05-27 JP JP14564198A patent/JP4201385B2/en not_active Expired - Fee Related
- 1998-05-27 BR BR9801709-8A patent/BR9801709A/en not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014200106A1 (en) | 2013-02-13 | 2014-08-14 | Evonik Industries Ag | Producing functional group-containing polysiloxane useful e.g. as component of dental impression compounds, comprises reacting terminal hydroxy functional, polysiloxane, alkoxysilanes, and water in the presence of Bronsted-acidic compound |
DE102014200106B4 (en) | 2013-02-13 | 2018-04-26 | Evonik Degussa Gmbh | Hardenable organomodified siloxanes produced by condensation |
Also Published As
Publication number | Publication date |
---|---|
CA2238556A1 (en) | 1998-11-27 |
US6103847A (en) | 2000-08-15 |
DE69831627T2 (en) | 2006-03-16 |
CA2238556C (en) | 2002-07-30 |
DE69831627D1 (en) | 2006-02-02 |
SG66469A1 (en) | 2000-07-18 |
KR100501141B1 (en) | 2005-11-01 |
EP0881249A3 (en) | 1999-01-27 |
KR19980087370A (en) | 1998-12-05 |
JP4201385B2 (en) | 2008-12-24 |
EP0881249A2 (en) | 1998-12-02 |
JPH10330490A (en) | 1998-12-15 |
BR9801709A (en) | 1999-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0885932B1 (en) | Hydrophilic polysiloxane compositions | |
US11725017B2 (en) | Method for preparing SiOC-linked polyether siloxanes branched in the siloxane part | |
EP0881249B1 (en) | Siloxane-polyether copolymers with unsaturated functionalities, and process for making them | |
EP0586240B1 (en) | Alkoxy endblocked polydiorganosiloxane and room temperature vulcanizable silicone elastomers made therefrom | |
US6197914B1 (en) | Method for preparing polyorganosiloxane resins that contain mono-and tetrafunctional units | |
JPH0623255B2 (en) | Method for producing perfluoroalkyl group-containing organopolysiloxane | |
JP2511046B2 (en) | Method for preparing liquid polydiorganosiloxane | |
JPH0517927B2 (en) | ||
US6353075B1 (en) | Polymerization of siloxanes | |
JPH06172535A (en) | Preparation of cluster azasilacycloalkyl- functional polysiloxane | |
US3445426A (en) | Pentavalent silane and tetravalent boron catecholates as polymerization catalysts | |
EP0628589A1 (en) | Process for the preparation of organopolysiloxanes | |
EP0499407B1 (en) | Crosslinkers and chain extenders for room temperature vulcanization or crosslinking of polymers | |
LeGrow et al. | Silicone polyether copolymers: synthetic methods and chemical compositions | |
EP0196169A2 (en) | Carboxylhydrocarbyl-substituted silicon compounds | |
EP2528927B1 (en) | Silicon polyethers and method of producing the same | |
US20030109659A1 (en) | Method for preparing polyorganosiloxanes by polymerisation catalysed by a catalytic system based of triflic acid derivatives | |
KR970006899B1 (en) | Catalyst for producing flnorosilicone polymers | |
EP2147949B1 (en) | Preparation of hydrolyzable group-containing organohydrogenpolysiloxane and organopolysiloxane derived therefrom | |
JP3925604B2 (en) | Method for producing (meth) acryloxy group-containing organopolysiloxane | |
JPH0912723A (en) | Polyether-modified polyorganosiloxane | |
CN1256284A (en) | Method for polymerization of siloxanes | |
US4281146A (en) | Method of neutralizing a halogen silicone compound | |
JPH0827272A (en) | Production of organosilicon resin | |
MXPA98004182A (en) | Copolimeros siloxano-polieter with unsaturated functionalities and process to manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 19990212 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: WITCO CORPORATION |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: YU, HUA Inventor name: LEWIS, KENRICK M. |
|
AKX | Designation fees paid |
Free format text: BE DE FR GB IT NL |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CK WITCO CORPORATION |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CROMPTON CORPORATION |
|
17Q | First examination report despatched |
Effective date: 20030818 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: GENERAL ELECTRIC COMPANY |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69831627 Country of ref document: DE Date of ref document: 20051027 Kind code of ref document: P |
|
REF | Corresponds to: |
Ref document number: 69831627 Country of ref document: DE Date of ref document: 20060202 Kind code of ref document: P |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20060622 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20140527 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20140529 Year of fee payment: 17 Ref country code: NL Payment date: 20140526 Year of fee payment: 17 Ref country code: IT Payment date: 20140527 Year of fee payment: 17 Ref country code: FR Payment date: 20140519 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20140530 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69831627 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150522 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150522 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20150601 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150522 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151201 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150601 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150601 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 |